Organic polyhydroxy compounds and derivatives



Patented Jan. 27, 1948 ORGANIC POLYHYDROXY COMPOUNDS 7 AND DERIVATIVESJoseph E. Bludworth and Donald P. Easter, Cumberland, Md., asslgnors toCelanese Corporation of America, a corporation of Delaware No Drawing.Application September 19, 1944, Serial No. 554,858

This invention relates to novel organic compounds and relates moreparticularly to 1-(3,4- dihydroxycyclohexyl) -1,2-dihydroxybutanone.

and to the ether and ester derivatives thereof, having the formulas vwherein R is an alkyl, cycloalkyl, aryl and aralkyl radical.

An object of our invention is the preparation of 1-(3,4-dihydroxycyclohexyl) -'1,2-dinydroxybutanone, and the novel etherand ester derivatives thereof.

, In accordance with the Diels-Alder reaction, the condensation ofacrolein with butadiene yields A -tetrahydrobenzaldehyde. On reactingthis'aldehyde with acetone in the presence of potassium hydroxide, ,8-(M-tetrahydrophenyl) -vinyl methyl ketone is formed,

. 2 ploying potassium permanganate as the oxidizing agent, the reactionis preferably allowed to proceed gradually, employing from 30. to partsby weight of a 1 to 7% aqueous solution of the potassium permanganate,the reactants being held at a temperature of 0 to 5 C. for 1 to 4 hoursand then allowed to rise to room temperature. The reaction may becompleted by heating at about 100 C. for 1 to 3 hours. The l-(3,4-dihydroxycyclohexyl) -l,2- dihydroxybutanone formed may beseparated from the reaction by extraction employing a suitablewaterimmiscible solvent such as diethyl ether.

When esterified with suitable organic acids or etherified with suitableetherifying agents, this polyhydroxy compound yields novel ether andester derivatives which are valuable for use as plasticizers. asintermediates in the preparation of higher molecular weight compoundsand for other industrial applications.

In order further to illustrate our invention but without being limitedthereto the following examples are given:

Example I 30 parts by. weight of p-(A -tetrahydrophenyl)-vinyl methylketone are suspended in 200 parts of water and cooled to 5 C. A solutionof 63 parts by weight of potassium permanganate in 1000 parts of wateris added over a period of one and one-half hours while maintaining thetemperature below 5 C. at all times. The mixture obtained is allowed towarm to room temperature, i. e. about 20 C.,. and then heated on a steambath for one hour. The precipitated manganese dioxide is filtered off,the filtrate saturated with sodium sulfate and then extracted withether. The ether extract is dried over an.- hydrous sodium sulfate andis then' evaporated to remove the ether. The residue comprises impure1-(3,4-dihydroxycyclohexyl) -1,2-dihydroxybutanone. The yield obtainedis over of theoretical. This compound is compatible with celluloseacetate and may be employed as a plasticizer therefor.

Example II 40.5 parts by weight of '1-(3,4-dihydroxycyclohexyl)-1,2-dihydroxybutanone are mixed with 80 parts by weight of aceticanhydride and boiled under reflux for one hour. After cooling, themixture is extracted with ether, the ether evaporated oil? and theresidue freed of water and acetic acid by heating at about 75 C. undermm. pressure in a slow current of air. The coming action thereon.

Example III To a solution of 218 parts by weight of 143,4-dihydroiqrcyclohexyl) -1,2-dihydroxybutanone in 7 350 parts absolutediethyl ether is added in small pieces 92 parts metallic sodium at sucha rate as to keep the ether slowly refluxing. When the addition ofsodium is complete, 252 parts of dimethyl sulfate are added withstirring, keeping the ether gently boiling. Cooling may be applied ifthe reaction tends to become violent during the initial stages of theaddition. After the dimethyl sulfate has been added, the mixture isstirred and refluxed for one hour. The sodium sulfate is filtered outand the ether evaporated from the filtrate. 'Ifhe residue,1-(3,4-dimethoxycyclohexyl) -1,2-dimethoxybutanone, can be purifled byrecrystallization from suitable organic solvents.

This procedure, yielding the completely methylated derivative, can bemodified by reducing the amount of 'dimethyl sulfate employed to yield,on reaction partially methylated products which contain unreactedhydroxyl groups.

The 1 (3,4 dihydroxycyclohexyl) 1,2 dihydroxybutanone may be esterifiedwith various other acids such as. for example. propionic, butyric,acrylic. succlnlc, phthalic and hexahydrobenzoic acid to producevaluable esters. As examples of ethers which may be formed there may bementioned the methyl. ethyl, propyl, butyl, iauryl. and benzyl ethersand the ethers of such poiyhydric alcohols as, for example, ethyleneglycol, propylene glycol and glycerol.

It is to be understood that the foregoing detailed description is givenmerely by way of illustration and that many variations may be madetherein without departing from the spirit of our invention.

Having described our invention, what we desire to secure by LettersPatent is:

1. 1-(3,4-diacetoxycyclohexyl) 1,2 diacetoxybutanone.

2. Process for the production of 1-(3,4-diacet- .oxycyclohexyl) 1,2diacetoxybutanone, which comprises reacting 1-(3,4-dihydroxycyclohexyl)-1,2-dihydroxybutanone with acetic anhydride until the hydroxy groupspresent are replaced by acetyl radicals.

3. Process for the production of 1-(3,4-diacetoxycyclohexyl) 1,2diacetoxybutanone, which comprises" acetylating 1 (3,4dihydroxycyclohexyl)-1,2-dihydroxybutanone with 1 to 3 parts by weightof acetic anhydride, the acetyiation being effected by refluxing the'mixture for from 1 to 8 hours. L

JOSEPH E. BLUDWORTH. DONALD P. EASTER.

REFERENCES orrn The following references are of record in the file ofthis patent:

UNITED STATES PATENTS Country Date Great Britain July 3, 1989 NumberNumber

